JP2015189912A - High density polyethylene resin particle, compound resin particle, foam particle, and foam molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide seed particles capable of further improving impact resistance at a high magnification without greatly decreasing heat resistance and slow-burning properties of a foam molded body.SOLUTION: High density polyethylene resin particles used for seed particles when polymerizing into seeds includes a mixed resin having the seed particles composed of 100 pts.wt. of a high density polyethylene and 20-100 pts.wt. of an ethylene copolymer where the high density polyethylene has a density of 935-960 kg/mand a softening point of 115-130°C, the ethylene copolymer is a copolymer of an ester monomer selected from acrylic acid alkyl ester and aliphatic saturated mono-carboxylic acid vinyl ester with ethylene, has 1-20 wt.% of a constituent derived from the ester monomer, and has a softening point of 75-110°C, the acrylic acid alkyl ester is selected from methyl acrylate and ethyl acrylate, and the aliphatic mono-carboxylic acid vinyl ester is selected from vinyl acetate and vinyl propionate.

Description

  The present invention relates to high-density polyethylene-based resin particles, composite resin particles, expanded particles, and expanded molded articles. More specifically, the present invention relates to a foamed molded article having improved mechanical properties even at high magnification, a foamed particle capable of giving the foamed molded article without the need for high-pressure foam molding, a composite resin particle for producing the foamed particle, and The present invention relates to high-density polyethylene resin particles used as seed particles when the composite resin particles are obtained by seed polymerization.

  It is known that a foam molded body made of polystyrene resin is excellent in rigidity, heat insulation, light weight, water resistance and foam moldability. Therefore, this foaming molding is widely used as a buffer material or a heat insulating material for building materials. However, the foamed molded body made of polystyrene resin has a problem of poor chemical resistance and impact resistance.

  On the other hand, it is known that a foam molded article made of a polyethylene resin is excellent in chemical resistance and impact resistance. Therefore, this foaming molding is used for automobile-related parts. However, since polyethylene-based resins have poor foaming agent retention properties, it is necessary to precisely control the foam molding conditions. Therefore, there is a problem that the manufacturing cost is high. In addition, the foam molded body has a problem that the rigidity is inferior to that of a foam molded body made of polystyrene resin.

  In order to solve the problems of the foamed molded article made of the polystyrene resin or the polyethylene resin, various foamed molded articles obtained from composite resin particles of polystyrene resin and polyethylene resin have been reported. This foam molded article combines the excellent rigidity and foam moldability of polystyrene-based resin with the excellent chemical resistance and impact resistance of polyethylene-based resin. However, there is a problem that the temperature dependence of the mechanical characteristics is high. In order to suppress this temperature dependency, a foam molded article using high-density polyethylene as a polyethylene resin has been reported (Japanese Patent Laid-Open No. 2012-25347).

JP 2012-25347 A

  According to the composite resin particles described in the above publication, it is possible to provide a foamed molded article having improved temperature dependence of mechanical properties. However, it is desired to provide seed particles, composite resin particles, and expanded particles that can further improve the impact resistance at high magnification without significantly lowering the heat resistance and retarded flame resistance of the expanded molded article.

Thus, according to the present invention, high-density polyethylene resin particles used as seed particles during seed polymerization,
The seed particles include a mixed resin of 100 parts by weight of high density polyethylene and 20 to 100 parts by weight of an ethylene copolymer,
The high density polyethylene has a density of 935-960 kg / m ³ and a softening temperature of 115-130 ° C .;
The ethylene copolymer is a copolymer of ethylene and an ester monomer selected from an alkyl acrylate ester and a vinyl aliphatic saturated monocarboxylate, and contains 1 to 20% by weight of an ester monomer-derived component; Having a softening temperature of ~ 110 ° C,
The alkyl acrylate is selected from methyl acrylate and ethyl acrylate;
High density polyethylene resin particles are provided, wherein the aliphatic saturated vinyl monocarboxylate is selected from vinyl acetate and vinyl propionate.

Furthermore, according to the present invention, 100 parts by weight of the high-density polyethylene resin derived from the high-density polyethylene resin particles and a styrene-based polymer obtained by impregnating and polymerizing the high-density polyethylene resin particles with a styrene monomer. Provided is a composite resin particle comprising a resin component comprising 100 to 500 parts by weight of a coalescence.
Moreover, according to this invention, the said composite resin particle is obtained by making it foam after impregnating a foaming agent, and the expanded particle which has a bulk density of 50-15 kg / m < ³ > is provided.
Furthermore, a foamed molded article obtained by subjecting the foamed particles to foam molding is provided.

According to the present invention, high density polyethylene resin particles are provided as seed particles for seed polymerization that can further improve the impact resistance at high magnification without significantly lowering the heat resistance and slow flammability of the foam molded article. it can. In addition, it is possible to provide a foamed molded article having further improved impact resistance at high magnification without significant reduction in heat resistance and slow flame retardancy.
When the ethylene copolymer has an MFR of 0.2 to 1.0 g / 10 min and contains 3 to 15% by weight of an ester-based monomer-derived component, the heat resistance and retarded flame resistance of the foamed molded product are greatly increased. It is possible to provide high-density polyethylene-based resin particles as seed particles for seed polymerization that can further improve impact resistance at high magnification without being reduced.
When the composite resin particles contain a flame retardant of 1.5 to 6.0 parts by weight with respect to 100 parts by weight of the resin, the heat resistance and retarded flame resistance of the foamed molded product are not significantly reduced, It is possible to provide composite resin particles that can further improve the impact resistance at the time.

When the flame retardant is a halogen-based flame retardant, it is possible to provide composite resin particles that can further improve the impact resistance at high magnification without significantly reducing the heat resistance and slow flame retardance of the foamed molded product.
Further containing a flame retardant aid, the flame retardant aid is dicumyl peroxide, 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane and cumene hydroperoxide When selected from the above, it is possible to provide composite resin particles that can further improve the impact resistance at high magnification without significantly reducing the heat resistance and retarded flame resistance of the foamed molded product.

It is a figure explaining the regulation method of the penetration temperature from a TMA curve.

In recent years, resin particles capable of providing a high-magnification foam molded body having heat resistance, slow flame retardancy and impact resistance while maintaining high productivity from the desire for further weight reduction and cost reduction of the foam molded body. It is desired.
Therefore, the inventors of the present invention reviewed the raw material of the foamed molded product. The foam-molded product is obtained by foam-molding composite resin particles produced by a so-called seed polymerization method in which seed particles are impregnated and polymerized with styrene. The inventors have found that the configuration of seed particles greatly affects the various physical properties.

For example, when only an ethylene-vinyl acetate copolymer is used as seed particles, when producing a high-magnification foam molded article, it is necessary to increase the amount of flame retardant in order to achieve a predetermined retarded flame retardancy. However, when the amount of the flame retardant is increased, the heat resistance is lowered.
In addition, when high-density polyethylene is used, predetermined heat resistance and slow flame retardance can be obtained even at high magnification, but impact resistance is reduced.
Furthermore, it is difficult to obtain predetermined heat resistance and slow flame retardance with linear low density polyethylene.
Furthermore, when polypropylene is used, it is possible to obtain the prescribed heat resistance, retarded flame resistance and impact resistance even at high magnification, but it is necessary to use a high vapor pressure during foam molding, resulting in reduced productivity. Will do.
In view of the above results, the inventors further studied various raw materials, and as a result, seed particles for a seed polymerization method containing a mixture of high-density polyethylene and a copolymer of ethylene and a specific type of ester monomer. High-density polyethylene resin particles as a high-impact impact resistance at high magnification without the need for foam molding at high vapor pressure, without significantly reducing the heat resistance and slow-flammability of the foam molding Surprisingly, the present invention has been found.

(High-density polyethylene resin particles: seed particles)
The seed particles of the present invention are high density polyethylene resin particles containing a mixed resin of high density polyethylene and an ethylene copolymer.
(1) High-density polyethylene High-density polyethylene is a resin made of an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms. Moreover, as said alpha olefin, a C3-C4 propylene and 1-butene are more preferable from a heat resistant viewpoint.

The high-density polyethylene used in the present invention is not particularly limited as long as it is a resin having a density of 935 to 960 kg / m ³ and a softening temperature of 115 to 130 ° C. A commercially available resin can be used. For example, it can be obtained from Tosoh, Braschem, Japanese polyethylene and the like.
When the density is less than 935 kg / m ³ , the heat resistance and slow flame retardance of the molded product may be lowered. When it is larger than 960 kg / m ³ , the foamability may be lowered or the impact resistance may be insufficient. A preferable density is 940 to 960 kg / m ³ , more preferably 946 to 955 kg / m ³ . When the softening temperature is less than 115 ° C., the heat resistance may be insufficient. When the temperature is higher than 130 ° C., a large amount of polymer powder may be generated in the production of composite resin particles by seed polymerization, or foamability may be insufficient. The preferred softening temperature is 118 to 128 ° C, more preferably 115 to 125 ° C.

(2) Ethylene Copolymer An ethylene copolymer is a copolymer of ethylene and an ester monomer selected from alkyl acrylate and vinyl aliphatic saturated monocarboxylate. Ester monomers are characterized by having —COO— bonds or —OCO— bonds in the molecule.
The alkyl acrylate ester is selected from methyl acrylate and ethyl acrylate, and the aliphatic saturated vinyl monocarboxylate is selected from vinyl acetate and vinyl propionate.

The ethylene copolymer is not particularly limited as long as the proportion of the ethylene-based polymer occupied by the ester-based monomer component is 1 to 20% by weight and the polymer has a softening temperature of 75 to 110 ° C. Commercially available resins can be used. For example, it can be obtained from Japanese polyethylene, Tosoh and the like.
When the proportion of the ethylene monomer-derived component derived from the ester monomer is less than 1% by weight, the effect of improving the slow flame retardancy may be insufficient. When it is larger than 20% by weight, the heat resistance may be lowered. A more preferable proportion is 5 to 15% by weight, and further preferably 3 to 10% by weight.
When the softening temperature is less than 75 ° C., heat resistance may be lowered. When it is higher than 110 ° C., the effect of improving the retarded flame property may be insufficient. A preferred softening temperature is 80 to 100 ° C, more preferably 80 to 95 ° C.

  The ethylene copolymer preferably has an MFR of 0.2 to 1.0 g / 10 min. When MFR is less than 0.2 g / 10 min, foaming variation may occur during foaming. If it is higher than 1.0 g / 10 min, the heat resistance may be reduced or the molded product may shrink. More preferable MFR is 0.2 to 0.8 g / 10 min, and further preferably 0.3 to 0.6 g / 10 min.

(3) Mixing ratio of high density polyethylene and ethylene copolymer The ethylene copolymer is contained in the mixed resin in a range of 20 to 100 parts by weight with respect to 100 parts by weight of the high density polyethylene. When the content of the ethylene copolymer is less than 20 parts by weight, the effect of improving the retardability may be insufficient. When the amount is more than 100 parts by weight, heat resistance and impact resistance may be lowered. The preferred content is 30 to 90 parts by weight, more preferably 40 to 75 parts by weight.

(4) Other components The seed particles may contain components (other components) other than the high-density polyethylene and the ethylene copolymer. Other components include colorants, nucleating agents, stabilizers, fillers (reinforcing materials), higher fatty acid metal salts, flame retardants, antistatic agents, lubricants, natural or synthetic oils, waxes, UV absorbers, weathering stabilizers. , Antifogging agents, anti-blocking agents, slip agents, coating agents, neutron shielding agents and the like. The content of other components is preferably 10% by weight or less based on the total amount of seed particles.

(5) Production method of seed particles The seed particles can be obtained by a known method. For example, a high-density polyethylene and an ethylene copolymer are melt-kneaded in an extruder and extruded to obtain a strand, and the resulting strand is cut in air, cut in water, and heated. And a granulating method. The high density polyethylene and the ethylene copolymer may be mixed by a mixer before being put into the extruder.
The seed particles are preferably cylindrical, oval (egg) or spherical. Moreover, in order to improve the filling property of the foamed particles obtained from the seed particles into the mold, the shape is more preferably oval or spherical.
The seed particles preferably have an average particle diameter of 0.5 to 1.4 mm.

(Composite resin particles)
(1) Configuration of Composite Resin Particle The composite resin particle of the present invention contains a high-density polyethylene resin and a resin component composed of a styrene polymer. The high density polyethylene resin is derived from high density polyethylene resin particles. The styrene polymer is derived from a styrene monomer impregnated and polymerized (seed polymerized) into high density polyethylene resin particles.
The styrene polymer is contained in the resin component at a ratio of 100 to 500 parts by weight with respect to 100 parts by weight of the high density polyethylene resin particles. When the content of the styrenic polymer is less than 100 parts by weight, the rigidity of the foamed molded product may be lowered. When content exceeds 500 weight part, the chemical resistance and impact resistance of a foaming molding may fall. A preferable content is 150 to 400 parts by weight, and a more preferable content is 200 to 350 parts by weight. Note that the content of the styrenic polymer substantially corresponds to the added amount of the styrenic monomer.

  Examples of the styrenic polymer include polymers derived from styrenic monomers such as styrene, α-methylstyrene, p-methylstyrene, and t-butylstyrene. Furthermore, the styrene polymer may be a component composed of a copolymer of a styrene monomer and another monomer copolymerizable with the styrene monomer. Examples of other monomers include polyfunctional monomers such as divinylbenzene, and (meth) acrylic acid alkyl esters that do not contain a benzene ring in the structure such as butyl (meth) acrylate. You may use these other monomers in the range which does not exceed 5 weight% in a styrene-type polymer.

The composite resin particles preferably contain a flame retardant. Examples of the flame retardant include known halogen flame retardants, phosphorus flame retardants, and inorganic flame retardants. Of these, halogen-based flame retardants such as brominated flame retardants, chlorinated flame retardants, and chlorinated bromine-containing flame retardants are preferred from the viewpoint of imparting high flame retardancy to foamed molded products in a small amount. Examples of halogen flame retardants include tris (2,3-dibromopropyl) isocyanurate, tetrabromocyclooctane, hexabromocyclododecane, trisdibromopropyl phosphate, tetrabromobisphenol A, tetrabromobisphenol A-bis (2,3- And dibromo-2-methylpropyl ether) and tetrabromobisphenol A-bis (2,3-dibromopropyl ether).
The flame retardant is preferably contained in an amount of 1.5 to 6.0 parts by weight with respect to 100 parts by weight of the resin component. When the content of the flame retardant is less than 1.5 parts by weight, the effect of improving flame retardancy may be insufficient. When the content exceeds 6.0 parts by weight, the chemical resistance, impact resistance, and heat resistance of the foamed molded product may be lowered. A preferable content is 1.5 to 4.0 parts by weight, and a more preferable content is 2.0 to 3.5 parts by weight.

The composite resin particles preferably contain a flame retardant aid in addition to the flame retardant. By including a flame retardant aid, the flame retardancy exhibited by the flame retardant can be further increased. As flame retardant aids, organic peroxidation of dicumyl peroxide, 2,3-dimethyl-2,3-diphenylbutane (also known as biscumyl), 3,4-dimethyl-3,4-diphenylhexane, cumene hydroperoxide Things.
The flame retardant aid is preferably contained in an amount of up to 50 parts by weight with respect to 100 parts by weight of the flame retardant. When the content of the flame retardant exceeds 50 parts by weight, the chemical resistance, impact resistance, and weather resistance of the foamed molded product may be lowered. A more preferable content is 10 to 40 parts by weight, and a still more preferable content is 15 to 25 parts by weight.
The shape of the composite resin particles is preferably cylindrical, substantially spherical or spherical, and the average particle diameter is preferably 0.6 to 1.8 mm. The shape is more preferably approximately spherical or spherical in order to improve the filling property of the expanded particles derived from the composite resin particles into the mold.

(2) Production Method of Composite Resin Particles Composite resin particles can be formed by a so-called seed polymerization method using high density polyethylene resin particles as seed particles. The seed polymerization method can be performed by the following procedure.
That is, seed particles, a styrene monomer, and a polymerization initiator as needed are dispersed in an aqueous suspension. A styrene monomer and a polymerization initiator may be mixed and used in advance.
Examples of the aqueous medium constituting the aqueous suspension include water and a mixed medium of water and a water-soluble solvent (for example, lower alcohol).

As the polymerization initiator, those generally used as an initiator for suspension polymerization of a styrene monomer can be used. For example, benzoyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, t-butylperoxy- Organic peroxides such as 3,5,5-trimethylhexanoate and t-butyl-peroxy-2-ethylhexyl carbonate. These polymerization initiators may be used alone or in combination of two or more.
The amount of the polymerization initiator used is preferably 0.1 to 0.9 parts by weight with respect to 100 parts by weight of the styrene monomer. If it is less than 0.1 parts by weight, it may take too much time to polymerize the styrene monomer. Use of a polymerization initiator exceeding 0.9 part by weight may lower the molecular weight of the polystyrene resin. A more preferable usage amount is 0.2 to 0.5 parts by weight.

A dispersant may be added to the aqueous suspension as necessary. The dispersant is not particularly limited, and any known dispersant can be used. Specific examples include hardly soluble inorganic substances such as calcium phosphate, magnesium pyrophosphate, sodium pyrophosphate, magnesium oxide. In addition, surfactants such as sodium dodecylbenzenesulfonate may be used.
Next, the obtained dispersion is heated to a temperature at which the styrene monomer does not substantially polymerize to impregnate the seed particles with the styrene monomer. The time for impregnating the styrene monomer inside the seed particles is suitably from 30 minutes to 2 hours. This is because if the polymerization proceeds before sufficient impregnation, a polymer powder of polystyrene resin is produced. The higher the temperature at which the styrenic monomer is not substantially polymerized, it is advantageous to increase the impregnation rate, but it is preferable to determine in consideration of the decomposition temperature of the polymerization initiator.

Next, the styrene monomer is polymerized. The polymerization is not particularly limited, but is preferably performed at 105 to 140 ° C. for 1.5 to 5 hours. The polymerization is usually carried out in an airtight container that can be pressurized.
The impregnation and polymerization of the styrene monomer may be performed in a plurality of times. By dividing into multiple times, the generation of polystyrene resin polymer powder can be minimized.
Composite resin particles can be obtained by the above process. The inventors believe that the obtained composite resin particles have a polystyrene resin-rich interior and a polyethylene resin-rich outer shell, and thus have a positive influence on the physical properties of the foamed molded product.
Composite resin particles containing a flame retardant and a flame retardant aid can be obtained by a method of impregnating seed particles with a flame retardant and a flame retardant aid together with a styrene monomer, a method of impregnating resin particles after polymerization, and the like.

(Foamed particles)
Expanded particles are particles obtained by foaming expandable particles after obtaining expandable particles by impregnating the composite resin particles with a foaming agent. Examples of the foaming agent include propane, n-butane, isobutane, n-pentane, isopentane, cyclopentane, hexane, dimethyl ether and the like. These foaming agents can be used alone or in admixture of two or more. The content of the foaming agent is preferably 5 to 25 parts by weight with respect to 100 parts by weight of the composite resin particles.

The expanded particles have a bulk density of 50 to 15 kg / m ³ . When the bulk density is less than 15 kg / m ³ , the closed cell ratio may be lowered when foamed, and the strength of the foamed molded product obtained from the pre-foamed particles may be lowered. On the other hand, when it is larger than 50 kg / m ³ , the effect of reducing the weight of the obtained foamed molded product may be small. A more preferable bulk density is 40 to 22 kg / m ³ .
Expandable particles can be obtained by impregnating a composite resin particle during or after polymerization with a foaming agent. This impregnation can be performed by a method known per se. For example, the impregnation during the polymerization can be performed by performing the polymerization reaction in a sealed container and press-fitting a foaming agent into the container. The impregnation after the completion of the polymerization is performed by press-fitting a foaming agent in a sealed container.
Furthermore, foaming of the expandable particles can be performed by a known method such as a method of heating the expandable particles in the container with water vapor.

(Foamed molded product)
The foamed molded body can be obtained by filling the foamed particles in a mold of a foam molding machine and heat-sealing the foamed particles while heating the foamed particles with water vapor. The expanded particles containing the seed particles have an advantage that high pressure is not required for the expanded molding conditions for obtaining the expanded molded article. Specifically, a foam-molded product can be obtained with water vapor having a pressure of 0.05 to 0.15 MPa, which is a general gauge pressure. Accordingly, since a foam molding machine for ordinary foaming can be used, the cost for obtaining a foam molded product can be reduced.
The foamed molded article is particularly excellent in shrinkage rate, flame retardancy and impact resistance.
Specifically, it is possible to provide a foamed molded article that exhibits a dimensional change rate of 1.5% or less when measuring dimensional changes at 80 ° C. in accordance with JIS K6767. Moreover, in the burning rate test method based on FMVSS 302, the foaming molding which shows a burning rate of 80 mm / min or less can be provided. Furthermore, the foaming molding which shows the falling ball impact value of 25 cm or more can be provided.

The foamed molded body preferably has a density of 50 to 20 kg / m ³ . When the density is less than 20 kg / m ³ , the strength may be lowered because the closed cell ratio increases. On the other hand, if it is greater than 50 kg / m ³ , the effect of weight reduction may be small. A more preferable density is 40 to 25 kg / m ³ .
The foamed molded product of the present invention can be used for various applications, but it can be used for bumper core materials, automotive cushioning materials such as door interior cushioning materials, electronic parts, various industrial materials including glass, food cushioning materials and transport containers, etc. It can be used for various applications. In particular, it can be suitably used for a vehicle cushioning material.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
The measuring methods of various physical properties in the following examples are described below.
<Density of high-density polyethylene>
The density is measured by a density gradient tube method in accordance with JIS K6922-1: 1998.

<MFR of high-density polyethylene and ethylene copolymer>
Melt mass flow rate (MFR) is a semi-auto melt indexer 2A manufactured by Toyo Seiki Seisakusho Co., Ltd. B) Measured by a method of measuring the time required for the piston to move a predetermined distance as described in Method B. The measurement conditions are as follows: sample 3 to 8 g, preheating 270 seconds, load hold 30 seconds, test temperature 190 ° C., test load 21.18 N, and piston moving distance (interval) 25 mm. The number of test of the sample is 3, and the average is the value of melt mass flow rate (g / 10 min).
<Melting point of high density polyethylene and ethylene copolymer>
Measured by the method described in JIS K7121: 1987 “Method for Measuring Transition Temperature of Plastic”. However, the sampling method and temperature conditions are as follows.
Using a differential scanning calorimeter device DSC 6220 (manufactured by SII Nano Technology), about 6 mg of the sample is filled so that there is no gap at the bottom of the aluminum measurement container. After filling, under a nitrogen gas flow rate of 20 mL / min, the temperature is lowered from 30 ° C. to −40 ° C. and held for 10 minutes. After holding, the temperature is raised from −40 ° C. to 220 ° C. (1st Heating) and held for 10 minutes. Next, a DSC curve is obtained when the temperature is lowered from 220 ° C. to −40 ° C. (Cooling), held for 10 minutes and then raised from −40 ° C. to 220 ° C. (2nd Heating). All the temperature increases / decreases are performed at a rate of 10 ° C./min, and alumina is used as a reference material. In this specification, the melting point is a value obtained by reading the temperature at the top of the melting peak observed in the 2nd Heating process using analysis software attached to the apparatus.

<Softening temperature of high-density polyethylene and ethylene-based copolymer>
Measured according to the method described in JIS K7196: 1991 “Method for testing softening temperature of thermoplastic film and sheet by thermomechanical analysis”.
That is, a resin sample is hot-pressed at 180 ° C. for 5 minutes to produce a disk plate-shaped test piece having a thickness of 1 mm and a diameter of 10 mm. Using a heat / stress / strain measurement device (product name “EXSTRAR TMA / SS6100” manufactured by SII Nano Technology), under a nitrogen atmosphere, a penetration test mode (needle tip φ1 mm, quartz probe) with a load of 500 mN The TMA curve is obtained by applying a needle to the test piece and increasing the temperature from 30 ° C. at a rate of temperature increase of 5 ° C./min. The obtained TMA curve is corrected by setting the quartz coefficient with the analysis software attached to the device, and the straight line portion that is recognized on the low temperature side is extended to the high temperature side than the indenter (needle) of the TMA curve starts to penetrate, and the penetration speed is The intersection between the maximum tangent and the extension to the low temperature side is defined as the penetration temperature, and the penetration temperature is defined as the softening temperature of the resin sample. A method for defining the penetration temperature from the TMA curve is shown in FIG.

<Bulk density of expanded particles>
The bulk density of the expanded particles is measured as follows. First, the expanded particles are filled in a graduated cylinder to a scale of 500 cm ³ . However, the graduated cylinder is visually observed from the horizontal direction, and if at least one expanded particle reaches the scale of 500 cm ³ , the filling is finished. Next, the weight of the expanded particles filled in the measuring cylinder is weighed with two significant figures after the decimal point, and the weight is defined as W (g). The bulk density of the expanded particles is calculated by the following formula.
Bulk density of expanded particles (kg / m ³ ) = W / 500 × 1000

<Density of foam molding>
The weight (a) and volume (b) of the test piece (example 75 × 300 × 35 mm) cut out from the foamed molded product (after being molded and dried at 50 ° C. for 4 hours or more) are each three or more significant figures. And the density (kg / m ³ ) of the foamed molded product is obtained from the formula (a) / (b).

<Heat dimensional change rate of foamed molded product>
The heating dimensional change rate of the foamed molded product is measured by the B method described in JIS K6767: 1999 “Foamed Plastic-Polyethylene Test Method”. Specifically, a test piece having a length of 150 mm, a width of 150 mm, and a height of 20 mm is cut out from the foamed molded body. On the surface of the test piece, three straight lines with a length of 50 mm directed in the vertical direction are written in parallel with each other at intervals of 50 mm, and three straight lines with a length of 50 mm directed in the horizontal direction are set with 50 mm in parallel with each other. Fill in every interval. After that, the test piece was left in a hot air circulating dryer at 80 ° C. for 168 hours and then taken out, and taken out for 1 hour in a standard state (20 ± 2 ° C., humidity 65 ± 5%). put. Next, the lengths of the six straight lines entered on the surface of the test piece are measured, and the arithmetic average value L1 of the lengths of the six straight lines is calculated. The degree of change S is calculated based on the following formula, and the absolute value of the degree of change S is defined as a heating dimensional change rate (%).
S = 100 × (L1-50) / 50
About heating dimensional change rate
◯ (good): 0 ≦ S <1.5; dimensional change rate was low, and dimensional stability was good. X (impossible): S ≧ 1.5; dimensional change was noticeable.
Is determined.

<Burning rate of foamed molded product>
The burning rate is measured by a method in accordance with the US automobile safety standard FMVSS 302.
The test piece is 350 mm × 100 mm × 12 mm (thickness), and it is assumed that the skin exists on at least two sides of 350 mm × 100 mm.
The burning rate is evaluated according to the following criteria.
○ (good): When the combustion speed is lower than 80 mm / min in the foam molded body with a predetermined density, or when the fire extinguishes before reaching the measurement start point in the foam molded body with the predetermined density. In this case, the burning rate is 0 mm / min (self-digesting).
X (impossible): In a foamed molded article having a predetermined density, when the combustion rate is greater than 80 mm / min

<Falling ball impact value of foam molding>
The falling ball impact strength is measured in accordance with the method described in JIS K7211: 1976 “General Rules for Hard Plastic Drop Weight Impact Test Method”.
After drying the foam-molded body having a predetermined density at a temperature of 50 ° C. for 1 day, a 40 mm × 215 mm × 20 mm (thickness) test piece (no skin on all six surfaces) is cut out from the foam-molded body.
Next, both ends of the test piece are fixed with clamps so that the distance between the fulcrums is 150 mm, and a hard ball having a weight of 321 g is dropped from a predetermined height onto the center of the test piece to check whether the test piece is broken or not. Observe.
The test piece was tested by changing the falling height (test height) of the hard sphere at 5 cm intervals from the lowest height at which all five specimens were destroyed to the highest height at which all were not destroyed, and the falling ball impact value (cm), ie 50% The fracture height is calculated by the following formula.
H50 = Hi + d [Σ (i · ni) /N±0.5]

The symbols in the formula mean the following:
H50: 50% fracture height (cm)
Hi: Test height (cm) when the height level (i) is 0 and the height at which the test piece is expected to break d: Height interval (cm) when the test height is raised or lowered
i: Height level when Hi is 0, and increases or decreases by 1 (i =... -3, -2, -1, 0, 1, 2, 3,...)
ni: Number of test specimens destroyed (or not destroyed) at each level, whichever data is used (if the number is the same, either may be used)
N: The total number of specimens that were destroyed (or not destroyed) (N = Σni), whichever data is used (if the number is the same, either may be used)
± 0.5: Use a negative number when using destroyed data, and use a positive number when using non-destructed data ○ (good): Falling ball impact value is 30 cm or more △ (possible): Falling ball impact Range where the value is 25 cm or more and less than 30 cm x (impossible): Falling ball impact value is less than 25 cm

<Chemical resistance of foamed molded products>
A flat rectangular plate-shaped test piece having a length of 100 mm, a width of 100 mm, and a thickness of 20 mm is cut out from the foamed molded article and left to stand at 23 ° C. and a humidity of 50% for 24 hours. In addition, a test piece is cut out from a foaming molding so that the upper surface whole surface of a test piece may be formed from the skin of a foaming molding. Next, 1 g of gasoline is uniformly applied to the upper surface of the test piece, and left for 60 minutes under the conditions of 23 ° C. and 50% humidity. Then, the chemical | medical agent is wiped off from the upper surface of a test piece, the upper surface of a test piece is visually observed, and it judges based on the following reference | standard.
About chemical resistance
○ (good): No change △ (possible): surface softening × (impossible): surface depression (shrinkage)
Is determined.

<Moldability>
The foamed particles are filled into a 300 mm × 400 mm × 30 mm mold of a foam molding machine, and the foamed particles are heat-fused while being heated by steam to have a top surface of 400 mm × 300 mm in width. Thus, a rectangular parallelepiped foam molded body having a thickness of 30 mm is obtained.
When heating with water vapor, the vapor pressure of the water vapor is changed from 0.08 MPa to 0.25 MPa in increments of 0.01 MPa, and water vapor is introduced for 20 seconds to perform a molding test.
As a result of the above molding, the obtained foamed molded product is evaluated according to the following criteria based on the lowest vapor pressure with a fusion rate of 90% or more. The lowest vapor pressure at which a 90% fusion rate is obtained is referred to as molding pressure adjustment.
◯ (good): A foamed molded product having a fusion rate of 90% or more at a vapor pressure of 0.15 MPa or less was obtained. It can be molded at low pressure and has high productivity.
X (unacceptable): Vapor pressure exceeding 0.15 MPa is necessary to obtain a foamed molded product having a fusion rate of 90% or more, and there is difficulty in productivity.
The fusion rate is measured by the following procedure.
A cutting line having a length of 300 mm and a depth of about 5 mm is put along the lateral direction with a cutter on the upper surface of the foamed molded body, and the foamed molded body is divided into two along this cutting line. And about the expanded particle of the fracture surface of the foamed molded product divided into two, the number of expanded particles broken in the expanded particle (a) and the number of expanded particles broken at the interface between the expanded particles (b) Measure and calculate the fusing rate based on the following formula.
Fusing rate (%) = 100 × (a) / [(a) + (b)]

Example 1
100 parts by weight of high density polyethylene (product number 09S53B, manufactured by Tosoh Corporation) having a density of 936 kg / m ³ , MFR 2.6 g / 10 min, melting point 123 ° C. and softening temperature 118 ° C., and ethylene-vinyl acetate copolymer (ethylene copolymer, Copolymer of aliphatic saturated vinyl monocarboxylate and ethylene: Nippon Polyethylene, product number LV115, MFR 0.3 g / 10 min, melting point 108 ° C., softening temperature 80 ° C., vinyl acetate-derived component content 4 wt%) 67 wt. Were put into a tumbler mixer and mixed for 10 minutes.
Next, this resin mixture is supplied to an extruder, melted and kneaded at a temperature of 230 to 250 ° C., granulated by an underwater cutting method, cut into an oval shape (egg), and high density polyethylene resin particles (seed particles). Got. The average weight of the high density polyethylene resin particles was 0.6 mg.

Next, in a 5 liter autoclave equipped with a stirrer, 40 g of magnesium pyrophosphate and 0.6 g of sodium dodecylbenzenesulfonate were dispersed in 2 kg of pure water to obtain a dispersion medium. 600 g of seed particles were dispersed in a dispersion medium at 30 ° C. and held for 10 minutes, and then heated to 60 ° C. to obtain a suspension. Furthermore, 300 g of styrene in which 0.6 g of dicumyl peroxide was dissolved as a polymerization initiator was added dropwise to this suspension over 30 minutes. After dropping, the seed particles were impregnated with styrene by holding for 30 minutes. After impregnation, the temperature was raised to 140 ° C., and polymerization was carried out at this temperature for 2 hours (first polymerization).
Next, 3 g of sodium dodecylbenzenesulfonate was dispersed in 20 g of pure water in a suspension lowered to 115 ° C. and dropped over 10 minutes, and then 1100 g of styrene in which 4 g of dicumyl peroxide was dissolved was added for 30 hours. It was added dropwise over a period of minutes. After dropping, the seed particles were impregnated with styrene by holding at 120 ° C. for 1 hour. After impregnation, the temperature was raised to 140 ° C., and this temperature was maintained for 3 hours for polymerization (second polymerization). As a result of this polymerization, composite resin particles could be obtained (weight ratio of seed particles to polystyrene 30/70).

Thereafter, the temperature of the reaction system was set to 60 ° C., and 50 g of tris (2,3-dibromopropyl) isocyanurate (manufactured by Nippon Kasei Co., Ltd.) as a flame retardant and dicumyl parper as a flame retardant aid were put in this suspension. 10 g of oxide was added. After the addition, the temperature of the reaction system was raised to 130 ° C., and stirring was continued for 2 hours to obtain flame retardant-containing composite resin particles.
Subsequently, it cooled to 30 degrees C or less, and took out the composite resin particle from the autoclave. 2 kg of composite resin particles, 2 liters of water, and 2.0 g of sodium dodecylbenzenesulfonate were placed in a 5 liter autoclave equipped with a stirrer. Further, 15 parts by weight (300 g, 520 mL) of butane (n-butane: i-butane = 7: 3) as a foaming agent was placed in an autoclave. Thereafter, the temperature was raised to 70 ° C. and stirring was continued for 4 hours, whereby expandable particles could be obtained. Thereafter, the mixture was cooled to 30 ° C. or lower, and the expandable particles were taken out from the autoclave and dehydrated and dried.

Next, the obtained expandable particles were pre-expanded to a bulk density of 25 kg / m ³ to obtain expanded particles. The obtained expanded particles were allowed to stand at room temperature (23 ° C.) for 1 day, and then placed in a molding die having a size of 400 mm × 300 mm × 30 mm.
Thereafter, 0.09 MPa water vapor is introduced for 20 seconds and heated, and then cooled until the maximum surface pressure of the foamed molded article is reduced to 0.01 MPa, whereby a density of 25 kg / m ³ with a fusion rate of 90% or more is obtained. The foamed molded product was obtained.
The appearance of the obtained foamed molded product was good.

Example 2
A foamed molded product having a fusion rate of 90% or more was obtained in the same manner as in Example 1 except that the bulk density of the foamed particles and the density of the foamed molded product were changed to 21 kg / m ³ . The appearance of the obtained foamed molded product was good.
Example 3
A foamed molded product having a fusion rate of 90% or more was obtained in the same manner as in Example 1 except that the bulk density of the foamed particles and the density of the foamed molded product were changed to 33 kg / m ³ . The appearance of the obtained foamed molded product was good.

Example 4
In the first polymerization, 800 g of seed particles are dispersed at 30 ° C. in the dispersion medium, 400 g of styrene monomer in which 0.8 g of dicumyl peroxide is dissolved is used in the first polymerization, and dicumyl peroxide is used in the second polymerization. Except for using 800 g of styrene monomer in which 4 g of styrene was dissolved, changing the bulk density of the expanded particles and the density of the expanded molded body to 33 kg / m ³ , and heating with 0.10 MPa of water vapor Produced a foamed molded article having a fusion rate of 90% or more in the same manner as in Example 1. The appearance of the obtained foamed molded product was good.
Example 5
Changing the high density polyethylene to a high density polyethylene (product number SEG7252 manufactured by Brasschem) having a density of 953 kg / m ³ , an MFR of 2.2 g / 10 min, a melting point of 131 ° C. and a softening temperature of 128 ° C., and a water vapor of 0.13 MPa A foamed molded article having a fusion rate of 90% or more was obtained in the same manner as in Example 1 except that it was used and heated. The appearance of the obtained foamed molded product was good.

Example 6
Changing high density polyethylene to high density polyethylene (product number HY350, manufactured by Nippon Polyethylene Co., Ltd.) having a density of 951 kg / m ³ , MFR of 2.5 g / 10 min, a melting point of 132 ° C., and a softening temperature of 122 ° C., and water vapor of 0.13 MPa A foamed molded article having a fusion rate of 90% or more was obtained in the same manner as in Example 1 except that heating was carried out using. The appearance of the obtained foamed molded product was good.
Example 7
An ethylene copolymer is a copolymer of an acrylic acid alkyl ester and ethylene (manufactured by Nippon Polyethylene Co., Ltd., product number A1100, MFR 0.4 g / 10 min, melting point 104 ° C., softening temperature 83 ° C., ethyl acrylate-derived component content 10 wt. %), A foamed molded article having a fusion rate of 90% or more was obtained in the same manner as in Example 1 except that the flame retardant aid was changed to biscumyl and heating was performed using water vapor of 0.08 MPa. The appearance of the obtained foamed molded product was good.

Example 8
The ethylene copolymer is a copolymer of acrylic acid alkyl ester and ethylene (manufactured by Nippon Polyethylene Co., Ltd., product number A1100), the weight ratio of high-density polyethylene and acrylic-containing copolymer is 60:40, flame retardant aid A foamed molded article having a fusion rate of 90% or more was obtained in the same manner as in Example 1 except that the heat treatment was performed using biscumir and heating with 0.09 MPa water vapor. The appearance of the obtained foamed molded product was good.
Example 9
Change the ethylene copolymer to Nippon Polyethylene Co., Ltd., part number LV430 (MFR 1.0 g / 10 min, melting point 89 ° C., softening temperature 73 ° C., vinyl acetate-derived component content 15% by weight), and flame retardant aid to biscumyl. In addition, a foamed molded article having a fusion rate of 90% or more was obtained in the same manner as in Example 1 except that heating was performed using water vapor of 0.08 MPa. The appearance of the obtained foamed molded product was good.

Example 10
Example 1 except that the ethylene copolymer is changed to Nippon Polyethylene, product number LV211 (MFR 0.3 g / 10 min, melting point 103 ° C., softening temperature 84 ° C., vinyl acetate-derived component content 6% by weight) Thus, a foamed molded product having a fusion rate of 90% or more was obtained. The appearance of the obtained foamed molded product was good.
Example 11
An ethylene copolymer is a copolymer of an acrylic acid alkyl ester and ethylene (manufactured by Nippon Polyethylene, product number A3100, MFR 3 g / 10 min, melting point 104 ° C., softening temperature 75 ° C., ethyl acrylate-derived component content 10% by weight) Example 1 except that the weight ratio of the high-density polyethylene and the acrylic-containing copolymer is 20:80, the flame retardant aid is changed to biscumyl, and heating is performed using 0.10 MPa of water vapor. Similarly, a foamed molded product having a fusion rate of 90% or more was obtained. The appearance of the obtained foamed molded product was good.

Example 12
An ethylene copolymer is a copolymer of an acrylic acid alkyl ester and ethylene (manufactured by Nippon Polyethylene Co., Ltd., product number A1100, MFR 0.4 g / 10 min, melting point 104 ° C., softening temperature 83 ° C., ethyl acrylate-derived component content 10 wt. %), High density polyethylene of density 951 kg / m ³ , MFR 2.5 g / 10 min, melting point of 132 ° C., softening temperature of 122 ° C. high density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., product number HY350), flame retardant aid is biscumyl A foamed molded article having a fusion rate of 90% or more was obtained in the same manner as in Example 1 except that the above was changed. The appearance of the obtained foamed molded product was good.

Comparative Example 1
As seed particles, particles made of only a polypropylene resin (manufactured by Prime Polymer Co., Ltd., product number F744NP) are used, and 800 g of seed particles are dispersed in a dispersion medium at 30 ° C. In the first polymerization, 0. 1 of dicumyl peroxide is added. Using 400 g of styrene monomer dissolved in 8 g, in the second polymerization, using 800 g of styrene monomer in which 4 g of dicumyl peroxide is dissolved and heating with 0.25 MPa water vapor Except for the above, a foamed molded article having a fusion rate of 90% or more was obtained in the same manner as in Example 1. The appearance of the obtained foamed molded product was good.
Comparative Example 2
As seed particles, use is made of particles consisting only of low-density polyethylene resin (manufactured by Nippon Polyethylene, product number NF444A, density 912 kg / m ³ , MFR 2 g / 10 min, melting point 121 ° C., softening temperature 93 ° C.), 0.08 MPa A foamed molded article having a fusion rate of 90% or more was obtained in the same manner as in Example 1 except that heating was performed using the water vapor. The appearance of the obtained foamed molded product was good.

Comparative Example 3
A foamed molded article having a fusion rate of 90% or more was obtained in the same manner as in Example 1 except that particles comprising only high-density polyethylene were used as seed particles and heating was performed using water vapor of 0.10 MPa. . The appearance of the obtained foamed molded product was good.
Comparative Example 4
Ethylene copolymer is a copolymer of methacrylic acid alkyl ester and ethylene (manufactured by Sumitomo Chemical Co., Ltd., product number WD201, MFR 2 g / 10 min, melting point 100 ° C., softening temperature 75 ° C., methyl methacrylate-derived component content 10% by weight) A foamed molded article having a fusion rate of 90% or more was obtained in the same manner as in Example 1 except that the heating was performed using water vapor of 0.10 MPa. The appearance of the obtained foamed molded product was good.

Comparative Example 5
Foaming with a fusion rate of 90% or more in the same manner as in Example 1 except that the weight ratio of the high-density polyethylene and the ethylene copolymer is changed to 10:90 and heating is performed using water vapor of 0.10 MPa. A molded body was obtained. The appearance of the obtained foamed molded product was good.
Comparative Example 6
Foaming with a fusion rate of 90% or more in the same manner as in Example 1 except that the weight ratio of the high-density polyethylene and the ethylene copolymer is changed to 20:80 and heating is performed using water vapor of 0.08 MPa. A molded body was obtained. The appearance of the obtained foamed molded product was good.
Comparative Example 7
Use as the seed particles particles made of only a high-density polyethylene resin (manufactured by Nippon Polyethylene Co., Ltd., product number HY350), change the bulk density of the expanded particles and the density of the expanded molded article to 33 kg / m ^3, and A foamed molded article having a fusion rate of 90% or more was obtained in the same manner as in Example 1 except that heating was performed using water vapor of 08 MPa. The appearance of the obtained foamed molded product was good.

Comparative Example 8
The fusion rate is 90% or more in the same manner as in Example 1 except that the high-density polyethylene resin is changed to a low-density polyethylene resin (manufactured by Nippon Polyethylene Co., Ltd., product number NF444A) and heated using 0.08 MPa water vapor. The foamed molded product was obtained. The appearance of the obtained foamed molded product was good.
The results obtained from the above Examples and Comparative Examples are shown in Tables 1-3.
In the table, A resin is an ethylene copolymer, B resin is high-density polyethylene, TAIC6B is tris (2,3-dibromopropyl) isocyanurate, BC is biscumyl, DCP is dicumyl peroxide, and AE is It means self-extinguishing.

From Tables 1 and 2, the following can be understood.
From Examples and Comparative Example 1, it can be seen that when only polypropylene is used instead of high-density polyethylene, a high pressure is required to obtain a foamed product having a desired multiple.
From Example and Comparative Example 3, it can be seen that when only high-density polyethylene is used, the falling ball impact value decreases.
From Examples and Comparative Example 4, it can be seen that when the ethylene copolymer is a copolymer of methacrylic acid alkyl ester and ethylene, the heating dimensional change rate increases.
From Examples and Comparative Example 5, it can be seen that if the high density polyethylene in the seed particles is too much, the burning rate increases.
From Example and Comparative Example 6, it can be seen that if the amount of high-density polyethylene in the seed particles is too small, the heating dimensional change rate increases.
From Examples 1, 5 and 6, it can be seen that the higher the density of the high-density polyethylene in the seed particles, the lower the heating dimensional change rate.

Claims (8)

High density polyethylene resin particles used as seed particles during seed polymerization,
The seed particles include a mixed resin of 100 parts by weight of high density polyethylene and 20 to 100 parts by weight of an ethylene copolymer,
The high density polyethylene has a density of 935-960 kg / m ³ and a softening temperature of 115-130 ° C .;
The ethylene copolymer is a copolymer of ethylene and an ester monomer selected from an alkyl acrylate ester and a vinyl aliphatic saturated monocarboxylate, and contains 1 to 20% by weight of an ester monomer-derived component; Having a softening temperature of ~ 110 ° C,
The alkyl acrylate is selected from methyl acrylate and ethyl acrylate;
The high-density polyethylene resin particles, wherein the aliphatic saturated vinyl monocarboxylate is selected from vinyl acetate and vinyl propionate.   The high-density polyethylene resin particles according to claim 1, wherein the ethylene copolymer has an MFR of 0.2 to 1.0 g / 10 min and contains 3 to 15 wt% of the ester monomer-derived component.   A styrene polymer obtained by impregnating and polymerizing 100 parts by weight of a high density polyethylene resin derived from the high density polyethylene resin particles according to claim 1 or 2, and a styrene monomer in the high density polyethylene resin particles. A composite resin particle comprising a resin component comprising 100 to 500 parts by weight.   The composite resin particle according to claim 3, wherein the composite resin particle contains 1.5 to 6.0 parts by weight of a flame retardant with respect to 100 parts by weight of the resin content.   The composite resin particle according to claim 4, wherein the flame retardant is a halogen-based flame retardant.   Further containing a flame retardant aid, the flame retardant aid is dicumyl peroxide, 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane and cumene hydroperoxide The composite resin particle according to claim 4 or 5 selected from. After impregnating a foaming agent to the composite resin particles according to any one of claims 3-6, obtained by foaming, foamed particles having a bulk density of 50~15kg / m ^3.   A foam molded article obtained by foam molding the foamed particles according to claim 7.

Images